JPS5936931B2 - Manufacturing method of mixed polycarbonate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The subject of the invention is a compound of the formula ■ Ho-Z→■ (■) in which z is a divalent aromatic group, preferably 6 to 30 C atoms.
0.05 to 0.5 mol % of diphenol and/or its chlorocarbonic ester containing an aromatic group containing (C)
chlorine or bromine, x is an integer from 7 to 24,
Y is OH or a halogen such as chlorine or bromine) together with up to 5 moles of phenol or a specific substituted phenol based on the number of moles of the structural unit Z,
This is a method for producing a mixed polycarbonate, characterized in that the reaction is carried out according to a solution method of polycarbonate synthesis.

The subject of the invention also includes mixed polycarbonates obtainable according to the process of the invention.

The mixed polycarbonates according to the invention have a weight average molecular weight (ylw) of at least 10,000, in particular from 10,000 to
200,000, particularly preferably 20,000 to 80,000
(measured by pre-standardized gel chromatography - π), and the formula [where E1 and E are the same or different, and the formula 1 (where VCR'111. and z represents a divalent aromatic group in the formula, and n represents at least 100,001 or 10,000 to 20,000 or 200 of the polycarbonate.
It is a polycarbonate having a weight average molecular weight (Mw) of VC-based polymerization degree of 00 to 80,000.

The mixed polycarbonate obtained by the method of the present invention is
It has good mold releasability, as well as good mechanical properties similar to known polycarbonates, especially at Vicat temperature (DIN 5346 Oy. is ASTM-D-1526-6).
5-TVC) has the property of not deteriorating at all.

A method for producing polycarbonate using a fatty acid or fatty acid chloride as a chain transfer agent is disclosed in JP-A-51-34992.
Known by the number.

It is also described therein that two or more types of molecular weight chain transfer agents can be used for polycarbonate production. However, Vc in Japanese Patent Publication No. 51-34992 does not describe the combination of phenols and fatty acids or fatty acid halides as chain transfer agents, or especially the simultaneous use of them. US Patent No. 3475
No. 873 describes the subsequent reaction of polycarbonates with acid halides and subsequent esterification with monohydroxy compounds.

The monomers used as chain transfer agents are inexpensive and readily available on the market and can be incorporated into polymers without difficulty according to the solution methods commonly used for polycarbonate production, thereby making them highly It is possible to produce polycarbonate that is easily released from the mold under economical conditions.

Diphenols of the formula preferably containing 6 to 30 C atoms are to be understood to include both mononuclear and polynuclear diphenols and those which contain heteroatoms and can be substituted. It is.

The following diphenols are suitable: hydroquinone, resorcinol, dihydroxydiphenyl, bis-(hydroxyphenyl)-alkanes, bis-(hydroxyphenyl).
-cycloalkane, bis-(hydroxyphenyl)-sulfide, pis-(hydroxyphenyl)-ether,
Bis-(hydroxyphenyl)-ketone, pis-(hydroxyphenyl)-sulfoxide, bis-(hydroxyphenyl)-sulfone and α,α5-bis-(hydroxyphenyl”)-diisopropylbenzene, and their nuclei. Alkylated and nuclear halogenated compounds. These and other suitable diphenols are described, for example, in U.S. Pat.
No. 028365, No. 2999835, No. 314817
No. 2, No. 3271365, No. 2991273, No. 3
No. 271367, No. 3280078, No. 301489
No. 1 and No. 2999846, German Publication No. 157
No. 0703, No. 2063050, No. 2063052, No. 2211956 and No. 2211957, French Patent No. 1561518, and publications H. ．． Sch
nell, Chemistry and Physics O
fPOlycarbOnates,bInter-Sc
ienceblishers9NewYOrk9l96
It is described in 4. Examples of preferred diphenols are: 4,4'-dihydroxy-diphenyl,
2,2-bis-(4-hydroxyphenyl)-propane, 2,4-bis-(4-hydroxyphenyl)-2-methylbutane, 1,1-bis-(4-hydroxyphenyl-cyclo-number) San, α-α7-bis-(4-hydroxyphenylin-p-diisopropylbenzene, 2,2-
Bis-(3-methyl-4-hydroxyphenyl)-propane, 2,2-bis-(3-chloro-4-hydroxyphenyl-propane, bis-(3,5-dimethyl-4-
hydroxyphenyl)-methane, 2,2-bis-(3,
5-dimethyl-4-hydroxyphenyl)-proban,
Bis-(3,5-dimethyl-4-hydroxyphenyl)
-sulfone, 2,4-bis-(3,5-dimethyl-4-
hydroxyphenyl)-2-methylbutane, 1,1-bis-(3,5-dimetal-4-hydroxyphenyl)-
cyclohexane, α,α5-bis-(3,5-dimethyl-4-hydroxyphenylon-p-diisopropylbenzene, 2,2-bis-(3,5-dichloro-4-hydroxyphenyno-propane and ,2-bis-(3,5
-dibromo-4-hydroxyphenyl)-propane.

Examples of particularly preferred diphenols are: 2,
2-bis-(4-hydroxyphenyl)-propane, 2
, 2-bis-(3,5-dimethyl-4-hydroxyphenyl)-propane, 2,2-bis-(3,5-dichloro-4-hydroxyphenyl-propane, 2,2-bis-(3, 5-dipromo4-hydroxyphenyl)-propane and 1,1-bis-(4-hydroxyphenyl)
- Cyclohexane.

Mixtures of any of the above diphenols can also be used.

To improve flow properties, a small amount, preferably 0.05 to 2
．． 0 mol % (based on the diphenol used) of a trifunctional or higher functional compound, especially a compound having 11C3 or more phenolic hydroxy groups, can be used in combination.

Some examples of compounds with three or more phenolic hydroxy groups that can be used are: phloroglucin, 4,6-dimethyl-2,4,6
-tri-(4-hydroxyphenyl)-heptane-2,
4,6-dimethyl-2,4,6-tri-(4-hydroxyphenyl)-heptane, 1,3,5-tri-(4-hydroxyphenyl)-benzene, 1,1,1-tri- (
4-hydroxyphenyl)-ethane, tri(4-hydroxyphenyl)-phenylmethane, 2,2-bis-[
4,4-bis-(4-hydroxyphenyl)-cyclohexyl]-propane, 2,4-bis-(4-hydroxyphenylisopropyl)-phenol, 2,6-bis-(21-hydroxy-5'- Methyl-benzyl)-4
-Methylphenol, 2-(4-hydroxyphenyl)
-2-(2,4-dihydroxyphenyl)-propane,
hexa-(4-(4-hydroxyphenylisopropyl)phenyl)ortote V phthalate, tetra-(4-hydroxyphenyl)-methane, tetra-(4-
(4-Hydroxyphenyl-isopropyl)-phenoxy)-methane and 1,4-bis((41,4-monodihydroxytriphenyl)-methyl)-benzene. Some examples of other trifunctional compounds are 2,4-dihydroxybenzoic acid, trimesic acid, cyanuric chloride and 3,3-
bis-(4-hydroxyphenyl)-2-oxo-2,
3-dihydroindole. The polycarbonates of the present invention can be produced essentially according to two known methods (H. Schnell, Chemist.
yandPh37SiCSOofPOly-CarbOn
ates″1P01ymerReviews2V01・
ζP゜27～La IntersciencePubl. ，
1964).

1. Solution method in the dispersed phase (so-called two-phase interfacial method): In this method, a diphenol of the formula is dissolved in an aqueous alkaline phase.

Here, the compound of the formula and the phenol and/or substituted phenol compound necessary for the production of the mixed polycarbonate of the present invention are added in an amount of 0.05 to 0.5 mol % of the compound of the formula based on the number of moles of the diphenol of the formula. and the phenolic compound is added in an amount of up to 5 mol %, in the form of an organic solvent solution or in neat form. The reaction with phosgene then takes place, preferably in the presence of an inert organic phase which dissolves the polycarbonate. The reaction temperature is 0 to 40°C. A compound of the required formula and a phenolic compound chain transfer agent can also be added in the form and amount π described above during the phosgenation process.

A third variant of the combined use of a compound of the formula and a phenolic chain transfer agent consists in adding the phenolic chain transfer agent before the phosgenation and adding the compound chain transfer agent of the formula at the end of the phosgenation. Become.

Suitable organic solvents for compounds of the formula are, for example, methylene chloride, chlorobenzene, mixtures of methylene chloride and chlorobenzene, acetone and acetonitrile.

The reaction can be assisted by a catalyst such as tributylamine or triethylamine.

Solution method in two homogeneous phases (also called pyridine method):
In this method, a diphenol of the formula is dissolved in an organic base such as pyridine, optionally with the addition of another organic solvent.
Dissolve and then proceed to step 1 above. The compound of the formula and the phenolic chain transfer agent necessary to make the polycarbonate of the invention are added at room temperature as described in K.

The amount added is based on the mo V number of the diphenol of the formula, the compound of the formula is 0.05 to 0.5 mol %, and the amount of the phenol compound chain transfer agent is up to $5 mol %. Next, a reaction with phosgene is performed.

The reaction temperature is 0-40°C. In addition to pyridine, suitable organic bases include, for example, triethylamine and tributylamine; suitable solvents are, for example, methylene chloride, chlorobenzene, and mixtures of methylene chloride and chlorobenzene. In methods 1 and 2VC above, the polycarbonate of the invention is isolated in a known manner.

Compounds of the formula suitable in the present invention include all C, -C
26 n-carboxylic acids, their halogenated derivatives and acid halides, i.e. perfluorononanoic acid, capric acid, myristic acid, palmitic acid, stearic acid, xerotic acid, and the corresponding acid chlorides and acid bromides. It is.

One compound of the formula or several compounds of the formula can be used together for the preparation of the polycarbonates of the invention.

Phenol chain transfer agents that can be used in combination with chain transfer agents of formulas suitable for the present invention include phenols p-tert-butylphenol, 2,4,6-tripromophenol, 2,4,6-tripromophenol or 2,6-
It is dimethylphenol.

Thus, in the solution process production of polycarbonates, the combined use of a phenolic chain transfer agent and a chain transfer agent of the formula according to the invention can be achieved either by adding the two chain transfer agents together prior to phosgenation or by adding them during the phosgenation process. or add it with
Alternatively, a phenol chain transfer agent is added before phosgenation, and a π-addition type chain transfer agent is added at the final stage of phosgenation.

When using the chlorocarbonate ester in addition to or in place of the diphenol of formula 1. Or 2. The amount of chain transfer agent required in the method can be calculated in a similar manner based on the number of structural units z according to the total amount of bisphenol and its chlorocarbonate of the formula. Anti-aging agents and anti-hydrolysis agents can be added to the mixed polycarbonates of the invention, which considerably increase the stability of the product according to this process.

For the purpose of improving the products of the invention, carbon black, diatomaceous earth, kaolin, clay, CaF2, CaCO,
, aluminum oxide, glass fibers and inorganic pigments can be added as fillers and also as nucleating agents. In the following example, ηRelfl′$. CH2
The value was measured at a concentration of 0.5% by weight in Cl2 and a temperature of 25°C.

Example 1 Mixed polycarbonate 2,2-bis- prepared using 0.5 mol % stearic acid chloride and 2.5 mol % p-tert-butylphenol as chain transfer agents.
A solution is prepared from 3.42 kg (15 moles) of (4-hydroxyphenyl)-propane (bisphenol A), 15 kg of 20% aqueous sodium hydroxide solution and 29.4 e of distilled water.

After adding 39.9e of methylene chloride, 0.0227kfI of stearic acid chloride was added at room temperature while stirring.
(0.075 mol) is added all at once. Next, 0.056 kg (0.375 mol) of p-tert-butylphenol is added. Phosgene 2.2 at 20-25°C
2? Kg, then triethylamine 0.015kg
is added and the mixture is stirred for an additional VC3O minute.

The upper aqueous phase is then separated and the organic phase is acidified and washed to remove the electrolyte. The polycarbonate is then precipitated with chlorobenzene after evaporating most of the methylene chloride from the organic phase. After grinding and drying at 130° C. in a vacuum drying chamber, the polycarbonate is granulated using a vacuum extruder.

ηReL=1.32, Bickert B temperature (DIN5346
(according to OllC) approximately 1460. Example 2 (Comparative Example) Mixed polycarbonate stearic acid chloride prepared using 2 mol % of stearic acid chloride and 1 mol % of p-tert-butylphenol as a chain transfer agent.
091k11P (0.3 mol = 2 mol%) and p-tert-butylphenol 0.0225 kg (0.1
The procedure is carried out in the same manner as described in Example 1, except that 5 mol = 1 mol %) is used.

ηRel=1.33, Bickert B temperature (DIN5346
According to O> about 13 VC0 Example 3 (comparative example) Polycarbonate produced using 4 mol % of stearic acid chloride and no other chain transfer agent π As described in Example 1, but using 4 mol % of stearic acid chloride and other carried out without a chain transfer agent.

ηRel=1.31 (NMR spectrum shows that stearic acid chloride is incorporated as a terminal group.

), Vicart B temperature {according to DIN 5346O) & $1
Lower than 35°C. Example 4 Mixed polycarbonate prepared using 0.2 mol% stearic acid and 2.7 mol% p-tert-butylphenol as chain transfer agents Example 1 with the following changes:
Proceed as described in: Instead of stearic acid chloride, a solution of 8.5 f (0.03 mol) of stearic acid in 400 mZ of methylene chloride is added dropwise.

The amount of p-tert-butylphenol is 60.75f
(2.7 mol%) Vc increases. ηRel=1.33,%C
Comparison of OOH < 0.01% physical properties The attached drawings show the mixed polycarbonates or polycarbonates obtained in Examples 1 to 4 (among them Examples 2 and 3 are comparative examples) and two other comparative examples, namely Same as Example 1 except p-
It is a drawing showing the mold release behavior of polycarbonates obtained using only tertiary-butylphenol (2.7 mol%) or only phenol (3.8 mol%).

The demolding behavior is read as demolding pressure, which shows that the lower the required demolding pressure at a given temperature, the better. The demolding pressure is measured as follows: a polycarbonate melt 159 is injection molded around a metal core with both length and diameter VC 35 mm.

After cooling to a specific temperature, the pressure required to release the injection mold from the metal core is measured. Some mechanical properties were determined using the mixed polycarbonates of Examples 1 and 2, as well as ηRel=1.26 to ηRel obtained as in Example 1 but using only p-tert-butylphenol as the chain transfer agent.
The results measured for polycarbonate No. 1.32 are shown in the table below.

[Brief explanation of drawings]

The drawings show the mold release behavior of the public polycarbonates or polycarbonates according to Examples 1 to 4 and two other comparative examples.

Claims (1)

[Claims] 1 A diphenol of the formula II HO-Z-OH (II) (wherein Z represents a divalent aromatic group) and/or its chlorocarbonate,
0.05 to 0.5 mol% based on the number of moles of structural unit Z Formula III ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (III) (In the formula, R' is the same and represents H or halogen, x is 7
up to 5 mol% of phenol, p-tert-butylphenol, 2,
1. A method for producing a mixed polycarbonate, which comprises reacting with 4,6-tribromophenol or 2,6-dimethylphenol according to a solution method for polycarbonate synthesis.